Petroleum Refining Chapter 4: Characterization

Chapter 4
Numerical Methods for Characterization and Properties Estimation of Petroleum Fuels
Introduction

Methods

Liquid Viscosity
1. The absolute (or dynamic) viscosity.
Defined as the ratio of shear resistance to the shear velocity gradient.
This ratio is constant for Newtonian fluids.
Expressed in Pa.s (poise)
Commonly used unit is mPa.s (centipoise, cP)
2. The kinematic viscosity.
Defined as the ratio between the absolute viscosity and the density.
Expressed in mm2/s (centistokes, cSt)
The liquid dynamic viscosities at 100 F and 210 F are used to characterize (heavy)
petroleum fractions.
When the viscosities are not known one of the following relations can be used to estimate
them. Abbott et al (1971) for example uses the Watson characterization factor (Kw) and API
gravity (A) to predict viscosity at 100 and 210 F as follows
100 = 4.39371 1.94733 + 0.12769 2
+ 3.2629. 104 2 1.18246. 102
+

(0.1716172 + 10.9943 + 9.50663. 102 2 0.860218 )

( + 50.3642 4.78231 )

210 = 0.463634 0.166532 + 5.13447. 104 2 8.48995. 103

+

(8.0325. 102 + 1.24899 + 0.19768 2 )

( + 26.786 2.6296 )

where
Kw = Watson characterization factor
A = gravity in degrees API
v100 = viscosity at 100 [mm2/s]
v210 = viscosity at 210 [mm2/s]
log = common logarithm (base 10)
notes:
Should not be used if Kw < 10 and A < 0.
Recommended for the following range;
0.5 < v100 < 20 mm2/s
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Copyright 2001-2015 Dr. Tareq Albahri, Chemical Engineering, Kuwait University

0.3 < v210 < 40 mm2/s

Average error about 20%.

Source: M. M. Abbott, T. G. Kaufmann and L. Domash. A correlation for predicting liquid

viscosities of petroleum fractions. The Canadian Journal of Chemical Engineering, Volume 49,
Issue 3, pages 379384, 1971 (DOI: 10.1002/cjce.5450490314)
Riazi method

Molecular Weight
Can be estimated with two different means (5% ave error)
1. From the normal BP and standard specific gravity.
Riazi method: for light fractions
(sp.gr. < 0.97 & Tb < 840 K).
M = 42.965 (Tb1.26007 S4.98308) [exp(2.097.10-4 Tb 7.78712 S + 2.08476.10-3 Tb S)]

Lee-Kesler: for heavy petroleum fractions (Tb > 600 K & 60 < MW < 650).

M 12272.6 9486.4 S T b (8.3741 5.9917 S )

107
222.466
(1 0.77084 S 0.02058 S 2 ) 0.7465

Tb
Tb

1012
17.3354
2
3 (1 0.80882 S 0.02226 S ) 0.32284
Tb
T b

where
M = Molecular weight [kg/kmol].
Tb = Normal boiling point [K].
S = Standard specific gravity.
2. From the viscosities at 210 F and 100 F and the standard specific gravity (ave. error is 10%).
(1.1228 S 1.2435) (3.47583.038 S )
0.6665
M 223.56 100
210
S

where
M = Molecular weight [kg/kmol].
v100 = viscosity at 100 F [mm2/s].
v210 = viscosity at 210 F [mm2/s].
S = Standard specific gravity.
Aniline Point (AP)
The equation of Albahri et al. gives the aniline point in C, Ri is the refractivity intercept, n is the
refractive index, d is liquid density at reference state of 20C and 1 atm. in g/cm3, Tb is the boiling
point in K, and I is an index in refractive index.
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Petroleum Refining Chapter 4: Characterization

Ri = n d/2
n = [(1+2I)/(1I)]0.5
I = 0.3824 (1.8Tb)-0.02269 SG0.9182
d = 0.98255 (1.8Tb)0.002016 SG1.0055
AP (C) = 9805.269 (Ri) + 711.85761(SG) + 9778.7069
(18)
Pseudo-Critical Constants for Petroleum Fractions.
To make use of the principle of corresponding states.
Use the method of Lee-Kesler (ave. error 10%)
1. Pseudo-Critical Temperature.

T C 189.8 450.6 S T b (0.4244 0.1174 S )

(14, 410 100,688 S )

Tb

where,
Tc = Pseudo-critical temperature [K].
Tb = Normal boiling point [K].
S = Standard specific gravity.
2. Pseudo-Critical Pressure
ln PC 5.68925

0.0566
S

4.12164 0.213426

103T b 0.436392

S
S2

11.819 1.53015

107T b 2 4.75794

S
S2

9.901

1010T b 3 2.45055 2
S

where,
Pc = Pseudo-critical pressure [bar].
ln = Napierian logarithm
Tb = Normal boiling point [K].
S = Standard specific gravity.
Acentric Factor for Petroleum Fractions.

For Tr < 0.8

7.904 0.1352K W 0.007465K W2

8.359T br

T br

1.408 0.1063K
W

T br

Tb
Tc

where
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Copyright 2001-2015 Dr. Tareq Albahri, Chemical Engineering, Kuwait University

= acentric factor.
Tbr = reduced boiling point temperature.
Kw = Watson characterization factor.

For Tr > 0.8 (use Edmister's equation)

3 x

(log Pc 1.0057)
7 1 x
where

Tb
Tc

and

Pc = Pseudo-critical pressure [bar].

Tc = Pseudo-critical temperature [K].
log = common logarithm (base 10)
Tb = Normal boiling point [K].

Specific Heat of Petroleum Fraction in the Ideal Gas State

H gp 2.325A BT CT 2 DT 3 ET 4 FT 5

C pgp 4.185B 2CT 3DT 2 4ET 3 5FT 4

T 1.8T

'

0.2846

B 0.35644 0.02972KW 0.29502

104
C
2.9247 1.5524KW 0.05543KW2 C '
2

5.0694

C ' 6.0283

107
1.6946 0.0844
D
3

12.8

10
S 0.885S 0.7 .104

11
K W
K W

Kw = Watson characterization factor

S = standard specific gravity

Flash Point, The API method (error 5C)

Tf

1
2.84947
0.02421
0.0034254

T 10

lnT 10

T10 = temperature at the 10% volume distilled point from ASTM D86 [k].
Liquid Enthalpy
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Petroleum Refining Chapter 4: Characterization

HL = A1 T 259.7 A2 T 2 259.72 A3 T 3 259.73

A1= 10 -3 1171.26 (23.722 24.907 ) KW 1149.8246535KW

13.817

A2= 10 -6 (1.0 0.82463KW ) 56.086

2.3653

A3= -10 -9 (1.0 0.82463KW ) 9.6757

Temperature (T)
Specific Gravity (SG)
Characterization Factor (Kw)

Vapor enthalpy

H V H L B1 T 0.8TC B2 T 2 0.64TC

B3 T 3 0.512TC
3

H O H
RTC

4
.
507

5
.
266

MW
RTC

248.46

B1 10 3 356.44 29.72 K W B4 295.02

253.46

B2 10 6 146.24 (77.62 2.772KW ) KW B4 301.42

B3 10 9 56.487 2.95B4

12.8

10.0
S 0.885S 0.7 10 4
B4
1.0 1.0
K
K
W

HL = Liquid Enthalpy of Petroleum Fractions

T = Temperature
Tc = Critical Temperature
R = Gas Constant
MW = Molecular Weight
= Acentric Factor
S = Specific Gravity
KW = Watson Characterization Factor
(Ho- H)/RTC = Pressure Effect on Enthalpy
Hv = Vapor Enthalpy of Petroleum Fractions

Calculation of Density by the Lee and Kesler Method

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Copyright 2001-2015 Dr. Tareq Albahri, Chemical Engineering, Kuwait University

Z Z 1 2.5138' 'w ' ( Z 2 Z 1 )

w w 1
Z Z 1 (Z 2 Z 1 )

w 2 w 1
b
b
b
B i b1i 2i 32i 43i
Tr Tr Tr
C i c1i

c 2 i c 3i

T r T r3
d 2i
Tr

D i d 1i

c 4i ( i2 i ) exp( 2i )
PrVri
Bi
Ci
Di
V ri
V ri
zi
1

2
5
3 2
Tr
Vri Vri Vri
T r V ri
l

PM
z l RT

Pressure for Saturation

Ps Pc m exp[f (T rm , m )]
f (T rm , m ) ln Pr0 m ln Pr0
ln Pr 0 5.92714

ln Pr 1 15.2518

6.09648
1.28862lnT rm 0.169347T rm6
T rm

15.6875
13.4721lnT rm 0.43577T rm6
T rm

Pressure Correction for Density

1 C ln

B P
B Ps

s
C 0.0861488 0.0344483m

B Pcm a k k 1
4

k 1

1 T r

1/ 3

Estimation of the pour point (page 172):

T EC 130.47S 2.971M

( 0.6120.474S )

v 100

( 0.310.333S )

Estimation of the Interfacial Tension of Petroleum fractions: (page 167)

293.15 1.232
]
Tcf
Kw

673.7[1

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Petroleum Refining Chapter 4: Characterization

Thermal Conductivities of Liquids: (page 132)

0.17 1.418 E 4T

Influence of Pressure on the Viscosity of Liquids (Kouzel's method):

log

M
( P Ps)(5.829 E 4Ms 0.181 1.479 E 4)
Ms

Specific Heats for liquid Petroleum Fractions (Lee Kessler 1975) Page 121:
Cp 4.185(0.35 0.055Kw )(0.3065 0.16734S T (1.467 *10 3 5.508 *10 4 S ))
l

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